CN107759621B - Bithiophene (selenophene) -modified photoelectric compound and preparation method and application thereof - Google Patents

Bithiophene (selenophene) -modified photoelectric compound and preparation method and application thereof Download PDF

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CN107759621B
CN107759621B CN201610682862.6A CN201610682862A CN107759621B CN 107759621 B CN107759621 B CN 107759621B CN 201610682862 A CN201610682862 A CN 201610682862A CN 107759621 B CN107759621 B CN 107759621B
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selenophene
chloroform
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邓丹
魏志祥
吕琨
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Jiaxing Hyper Optoelectronics Technology Co ltd
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Beijing Institute of Nanoenergy and Nanosystems
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Abstract

The invention relates to a preparation method and application of a soluble solution processing organic photovoltaic compound taking bithiophene (selenophene) and thiophene (selenophene) as pi-bridges, wherein the structural formula of the soluble solution processing organic photovoltaic compound is shown as a formula I. Based on the pi bridge, the compound of the invention selects an organic photoelectric compound with proper D and A units, has low exciton confinement energy and can effectively reduce the highest occupied electron orbital energy level of molecules, so that a high-efficiency material can obtain high open-circuit voltage. The compound of the invention is used as a donor material of an active layer of an organic solar cell, and the maximum open-circuit voltage of the compound exceeds 1V. The battery energy conversion efficiency of the positive structure is over 10 percent and the battery energy conversion efficiency of the inverted device structure reaches 11.5 percent without any additive and thermal and solvent annealing treatment by taking the fluorinated receptor unit as an end group, so that the battery energy conversion efficiency has important application value.

Description

Bithiophene (selenophene) -modified photoelectric compound and preparation method and application thereof
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a photoelectric compound containing bithiophene (selenophene) and thiophene (selenophene) as pi-bridge modification, and a preparation method and application thereof.
Background
Solar cells are one of the inexhaustible clean energy sources, namely, solar energy, and are used effectively. Compared with inorganic solar cells, organic solar cells have the advantages of abundant raw materials, light weight, flexibility, foldability, adoption of large-area printing process and the like, and thus have attracted extensive attention. Compared with polymer solar cells, solution processable organic small molecule solar cells have been developed rapidly in recent years due to the clear molecular structure without molecular weight distribution, but the efficiency of the organic small molecule solar cells is higher than 10% and the number of materials is very few.
Therefore, the molecular structure design is adopted to obtain the novel organic photoelectric compound with lower Highest Occupied Molecular Orbital (HOMO) energy level of electrons, better matching between absorption spectrum and solar spectrum, more ideal appearance and higher energy conversion efficiency, and is of great importance to the application of the whole organic photovoltaic field.
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a novel organic photovoltaic compound for a solar cell having high efficiency and high open circuit. The compound of the invention takes bithiophene (selenophene) and thiophene (selenophene) with high mobility as a pi bridge or a part of the pi bridge, and proper D and A units are selected to ensure that the compound has low exciton confinement energy and can effectively reduce the highest occupied electron orbital energy level of molecules, so that a high-efficiency material can obtain high open-circuit voltage.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic photovoltaic compound for a solar cell, having the structure shown in formula I below:
Figure GDA0001113880950000021
wherein the content of the first and second substances,
R1-R4can be independently selected from H and C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy, C1-C30Halogenated or non-halogenated mercapto groups, C1-C30Halogenated or non-halogenated cycloalkyl radicals, C1-C30Halogenated or non-halogenated carbonyl groups, C1-C30Halogenated or non-halogenated ester group and C1-C30Halogenated or non-halogenated sulfone group, in which R1-R6May be the same or different. X1、X2May be independently selected from a sulfur, oxygen or selenium atom, wherein X1、X2Which may be the same or different, D is a donor unit and A is an acceptor unit.
For example, formula II may be specifically as follows:
Figure GDA0001113880950000022
in detail, halo means halogen (F, Cl, Br, I) substitution.
The compound of the invention takes bithiophene (selenophene) and thiophene (selenophene) with high mobility as a pi bridge or a part of the pi bridge, and proper D and A units are selected to ensure that the D and A units have low exciton confinement energy and can effectively reduce the highest occupied electron orbital energy level of molecules, so that the high-efficiency material can obtain high open-circuit voltage.
Donor units that can be used in the present application include, but are not limited to:
Figure GDA0001113880950000031
wherein R is5Can be independently selected from C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy, C1-C30Halogenated or non-halogenated mercapto groups, C1-C30Halogenated or non-halogenated cycloalkyl radicals, C1-C30Halogenated or non-halogenated carbonyl groups, C1-C30Halogenated or non-halogenated aliphatic radical, C1-C30A halogenated or non-halogenated sulfone group; x3、X4Independently selected from the group consisting of sulfur, oxygen or selenium atoms.
Receptor units that can be used in the present application include, but are not limited to:
Figure GDA0001113880950000041
wherein R is6、R7Can be independently selected from C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy, C1-C30HalogenatedOr non-halogenated mercapto group, C1-C30Halogenated or non-halogenated cycloalkyl radicals, C1-C30Halogenated or non-halogenated carbonyl groups, C1-C30Halogenated or non-halogenated aliphatic radical, C1-C30Halogenated or non-halogenated sulfone groups.
In certain embodiments, the compound of formula I is selected from one of the following structures:
Figure GDA0001113880950000042
Figure GDA0001113880950000051
Figure GDA0001113880950000061
Figure GDA0001113880950000071
Figure GDA0001113880950000081
wherein R is1To R4Can be independently selected from H and C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy, C1-C30Halogenated or non-halogenated mercapto groups, C1-C30Halogenated or non-halogenated cycloalkyl in which Rm(m-1-4) may be the same or different. X1-X4Can be independently selected from sulfur, oxygen, or selenium atoms, wherein X1-X4May be the same or different.
In certain embodiments, the compound of formula I is selected from one of the following structures:
Figure GDA0001113880950000082
Figure GDA0001113880950000091
Figure GDA0001113880950000101
Figure GDA0001113880950000111
Figure GDA0001113880950000121
the invention also provides a preparation method of the compound, which is characterized in that the dialdehyde-based end group compound and the end group receptor unit are subjected to Kloevenger (knoevenagel) condensation reaction to prepare the compound.
Preferably, the preparation method comprises the following steps:
(1) under the protection of inert gas, adding a pi-bridge monomer, a trimethyl tin substituted donor unit and a catalyst into an organic solvent, and heating to react to obtain a dialdehyde end group precursor;
(2) and adding the dialdehyde end group precursor, the acceptor unit and the catalyst into a solvent for reaction to obtain the target compound.
The reaction process is as follows:
Figure GDA0001113880950000122
preferably, the inert gas in step (1) is nitrogen or argon.
Preferably, the pi-bridge monomer is alkylated bithiophene and thiophene/selenophene, or the monoaldehyde-terminated bromides of bithiophene and thiophene/selenophene (i.e., the monoaldehyde-terminated bromides of alkylated bithiophene and thiophene, bithiophene and selenophene, and selenophene and thiophene), which may be specifically: 1 of 5-bromo-3, 6-dihexylthieno [3, 2-b ] thiophene-2-carbaldehyde (formula 1), 5- (5-bromo-6-hexyl [3, 2-b ] thiophen-2-yl) -4-hexylthiophene-2-carbaldehyde (formula 2), 5- (5-bromo-6-hexyl [3, 2-b ] thiophen-2-yl) -4-hexylselenophene-2-carbaldehyde (formula 3), and 5- (5-bromo-6-hexyl [3, 2-b ] selenophen-2-yl) -4-hexylselenophene-2-carbaldehyde (formula 4).
Figure GDA0001113880950000131
Preferably, the trimethyltin-substituted donor unit may be 1 of the following:
Figure GDA0001113880950000132
wherein R is5Is H, C6-C12Halogenated or non-halogenated alkyl, C6-C12Halogenated or non-halogenated alkoxy, C6-C12Halogenated or non-halogenated mercapto groups, C6-C12Halogenated or non-halogenated cycloalkyl radicals, C6-C12Halogenated or non-halogenated carbonyl groups, C6-C12Halogenated or non-halogenated aliphatic radical, C6-C12Halogenated or non-halogenated sulfone groups.
Preferably, the catalyst is Pd (PPh)3)4。
Preferably, the solvent is toluene.
Preferably, the molar ratio of the pi-bridge monomer to the trimethyltin-substituted donor unit is from 2 to 4: 1.
Preferably, the molar amount of catalyst is from 5% to 10% of the pi-bridged monomer.
Preferably, the volume of the solvent toluene used in step (1) is between 10 and 100mL/mmol relative to the amount of trimethyltin substituted donor units.
Preferably, the heating reaction temperature is 80-100 ℃, and the reaction time is 12-48h, preferably 24-48 h.
Preferably, after the reaction in step (1) is completed, the reaction solution is concentrated and then purified by column chromatography.
Preferably, the concentration can be performed using rotary evaporation.
Preferably, the column chromatography uses a mixed solvent of dichloromethane and petroleum ether as an eluent.
Preferably, the molar ratio of the dialdehyde end group precursor to the acceptor unit in step (2) is 1: 1-15.
Preferably, the catalyst can be one or a mixture of more than two of triethylamine, piperidine or pyridine.
Preferably, the catalyst is used in a molar amount of 5 to 20% relative to the dialdehyde end-group precursor.
Preferably, the reaction temperature is 25-80 ℃ and the reaction time is 1-3 days.
Preferably, after the reaction in step (2) is finished, the reaction solution is concentrated, purified by a column, and then recrystallized to obtain the target compound.
Preferably, the concentration is carried out using rotary evaporation.
Preferably, the column chromatography uses a mixed solvent of chloroform and petroleum ether as an eluent.
Preferably, the recrystallization is performed using a mixed solvent of chloroform and methanol.
It is also an object of the present invention to provide a pi bridge monomer having the structure shown in formula II below:
Figure GDA0001113880950000151
wherein the content of the first and second substances,
R1-R4can be independently selected from H and C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy, C1-C30Halogenated or non-halogenated mercapto groups, C1-C30Halogenated or non-halogenated cycloalkyl radicals, C1-C30Halogenated or non-halogenated carbonyl groups, C1-C30Halogenated or non-halogenated aliphatic radical, C1-C30Halogenated or non-halogenated sulfone groups. Wherein R is2-R4May be the same or different. X1、X2May be independently selected from a sulfur, oxygen or selenium atom, wherein X1、X2May be the same or different.
The pi-bridge monomers of the invention may be, for example:
Figure GDA0001113880950000152
the invention also aims to provide a preparation method of the pi-bridge monomer, which is mainly prepared by coupling and brominating boric acid ester of bithiophene or bithiophene and bromide of monoaldehyde-substituted thiophene or selenophene.
Preferably, the preparation method of the pi bridge monomer comprises the following steps:
(1) under the protection of inert gas, reacting boric acid ester of bithiophene or boric acid ester of bithiophene with bromide of monoaldehyde substituted thiophene or selenophene, toluene, water, tetrahydrofuran and NaHCO3，Pd(PPh3)4Adding a catalyst into a toluene solvent for reaction to obtain a mono-aldehyde coupled compound;
(2) and (2) adding N-bromosuccinimide (NBS) into the mixed solution of the compound with the single aldehyde end group coupling obtained in the step (1), acetic acid and chloroform for reaction to obtain the pi bridge monomer.
For example, the pi-bridge monomers of the present invention can be synthesized by the following process:
Figure GDA0001113880950000161
preferably, the inert gas in step (1) is nitrogen or argon.
Preferably, the molar ratio of the borate of the bithiophene or diselenophene to the bromide of the monoaldehyde-substituted thiophene or selenophene is from 1:1 to 2.
Preferably, NaHCO3The mol ratio of the bromide of the single aldehyde substituted thiophene or selenophene is 3-10: 1.
Preferably Pd (PPh)3)4The molar amount of the compound is 2 to 10 percent of the bromide of the single aldehyde substituted thiophene or selenophene.
Preferably, the toluene solvent is used in an amount of 1-10mL/mmol relative to the monoaldehyde-substituted thiophene or selenophene.
Preferably, the ratio of toluene: water: the volume ratio of the tetrahydrofuran is 1:1: 1-10.
Preferably, the reaction temperature is 30-90 ℃ and the reaction time is 1-7 days.
Preferably, after the reaction in step (1) is finished, the reaction solution is washed with water and concentrated, and then is purified by a column.
Preferably, the concentration can be performed using rotary evaporation.
Preferably, the column chromatography uses a mixed solvent of dichloromethane and petroleum ether as an eluent.
Preferably, the molar ratio of NBS to bromide of monoaldehyde-substituted thiophene or selenophene in step (2) is 1-1.2: 1.
Preferably, the volume ratio of acetic acid to chloroform is 0.1-3: 1.
Preferably, the amount of chloroform is 5-50mL/mmol relative to the monoaldehyde-substituted thiophene or selenophene.
Preferably, the reaction temperature is-10-25 ℃, and the reaction time is 4-48 hours.
Preferably, after the reaction in step (2) is finished, the reaction solution is extracted and washed with water, and then purified by column chromatography to obtain the target compound.
Preferably, the extraction is performed with chloroform.
Preferably, the column chromatography uses a mixed solvent of dichloromethane and petroleum ether as an eluent.
The acceptor unit may be synthesized using techniques known in the art. For example, it can be synthesized by the following procedure:
Figure GDA0001113880950000171
wherein Y isnH or F (n-1-4), YnMay be the same or different. Specific synthetic procedures can be found in the literature (J.Med.chem.,16(12), 1334-1337).
It is a further object of the present invention to provide the use of the compounds according to the invention in the field of photovoltaic devices, in particular as active layer donor/acceptor materials for solar cells.
On the basis of the pi bridge, the organic photoelectric compound obtained by selecting proper D and A units has low exciton confinement energy and can effectively reduce the highest occupied electron orbital energy level of molecules, so that a high-efficiency material can obtain high open-circuit voltage. The compound based on the invention is used as a donor material of an active layer of an organic solar cell, and the maximum open-circuit voltage of the compound is more than 1V. The fluorinated acceptor unit is used as an end group, and the cell energy conversion efficiency of the forward structure is over 10% and the cell energy conversion efficiency of the inverted device structure is up to 11.5% without any additive, solvent or thermal annealing treatment, so that the fluorinated acceptor unit has an important application value in the field of photovoltaic devices.
Drawings
FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of M1 in a chloroform solution and in a thin film state;
FIG. 2 is a graph showing the UV-VIS absorption spectrum of M2 in a chloroform solution and in a thin film state;
FIG. 3 is a graph showing the UV-VIS absorption spectrum of M3 in a chloroform solution and in a thin film state;
FIG. 4 is a graph showing the UV-VIS absorption spectrum of M4 in a chloroform solution and in a thin film state;
FIG. 5 is a cyclic voltammogram measured by the electrochemical methods M1 and M2;
FIG. 6 is a cyclic voltammogram measured by the electrochemical methods M3 and M4;
FIG. 7 shows the structure of the forward device as ITO/PEDOT: PSS/M1: PC70J-V curve of soluble organic micromolecule solar cell device of BM/Ca/Al;
FIG. 8 shows the forward structure of ITO/PEDOT: PSS/M2: PC70J-V curve of soluble organic micromolecule solar cell device of BM/Ca/Al;
FIG. 9 shows the structure of an inversion device of ITO/ZnO/M3 PC70J-V curve of soluble organic small molecule solar cell device of BM/MoOx/Ag;
FIG. 10 shows the structure of an inversion device of ITO/ZnO/M4 PC70Soluble organic small of BM/MoOx/AgJ-V curve of molecular solar cell device.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1: synthesis of optoelectronic Compounds M1, M2, M3 and M4.
An organic photoelectric compound for a solar cell, the chemical structure of the compound is shown as formula (I), wherein more specific structures are shown as follows:
Figure GDA0001113880950000191
wherein X is1＝X2＝X3＝X4＝S，
Figure GDA0001113880950000192
R2＝R4＝C6H13，R3The specific structure after H is as follows:
Figure GDA0001113880950000193
Figure GDA0001113880950000201
preparation and Synthesis of optoelectronic Compound M1
The method mainly comprises the following steps:
synthesis of ① pi-bridged monomer 5- (5-bromo-6-hexyl [3, 2-b ] thiophen-2-yl) -4-hexylthiophene-2-carbaldehyde:
Figure GDA0001113880950000211
② Synthesis of intermediate dialdehyde end group and target compound M1
Figure GDA0001113880950000212
③ specific steps for the synthesis of each compound:
compound 3: pb (PPh) under nitrogen protection3)4(5% mmol) was added to Compound 1(3g, 8.57mmol), Compound 2(2.5g, 9.12mmol), NaHCO3After bubbling (2.16g, 25.7mmol) in a mixed solution of tetrahydrofuran (48ML), toluene (16ML) and deionized water (16ML) for 20 minutes, the temperature of the mixed solution was raised to 85 ℃ and reacted for 48 hours. And (3) carrying out rotary evaporation and concentration on reaction liquid, wherein petroleum ether: the eluent, dichloromethane ═ 1:1, was passed through a column and purified to yield a yellow solid (3g, 84%).
Compound 4: NBS (1.28g, 7.2mmol) was added portionwise to a mixed solution of Compound 3(3g, 7.2mmol) in chloroform (50mL) and acetic acid (50mL) in an ice-water bath. After the addition was completed, the reaction solution was warmed to room temperature for reaction overnight. After the reaction, the reaction mixture was poured into 50mL of chloroform, and the organic phase was washed with water three times, respectively, and saturated NaHCO was added3Washed three times with water and three more times, and the washed organic phase was dried over MgSO 4. And (3) carrying out rotary evaporation and concentration on reaction liquid, wherein petroleum ether: the eluent, dichloromethane ═ 1.5:1, was passed through a column and purified to yield a yellow solid (3g, 84.3%).
Compound 6: pd (PPh) under nitrogen protection3)4To a solution of compound 4(496mg, 1mmol) and compound 5(453mg, 0.5mmol) in dry toluene (40 mL). After bubbling with air for 20 minutes, the temperature of the mixture was raised to 100 ℃ and the reaction was carried out for 48 hours. After the reaction liquid is concentrated by rotary evaporation, the crude product adopts petroleum ether: the eluent, dichloromethane ═ 2:3, was passed through the column to afford the product as a red solid (501mg, 71%).
Target compound M1: under a nitrogen atmosphere, compound 6(200mg, 0.14mmol), 1, 3-dimethylpyrimidine-2, 4, 6(1H, 3H, 5H) -trione (218mg, 1.4mmol) and piperidine (0.59mg, 0.007mmol), which is a catalyst, were added to 30mL of dry chloroform and reacted at room temperature for 24 hours. Methanol was added to precipitate, and the mixture was centrifuged, and the solid portion was dissolved in chloroform, washed with water three times, and dried over anhydrous magnesium sulfate. The organic phase was rotary evaporated to remove the solvent, and the mixture was dried in petroleum ether: chloroform at a volume ratio of 1:2 as eluent, and separating the product by silica gel column chromatography. The product was recrystallized from chloroform and methanol, dichloromethane to give the product as a black solid (120mg, 50.2%).
Synthesis of optoelectronic Compound M2
Figure GDA0001113880950000221
Synthesis of target compound M2 target compound M2 was analogous to the synthesis of compound M1. The adopted catalyst is also piperidine, and the eluting agent adopts petroleum ether: chloroform was obtained in a mixed solvent of 1:2, and the yield of the obtained product was 60%.
Synthesis of optoelectronic Compound M3
Figure GDA0001113880950000231
Compound 8: tetrabutylacetoacetate (1.53g) was added to 4-fluorophthalic anhydride (1.4g), acetic anhydride (4.5mL) and triethylamine (2.5mL), stirred at room temperature for 24 hours, ice (3.3g) and concentrated hydrochloric acid (2.91 mL) were added thereto, and after stirring for 10 minutes, 12.3mL of 5M hydrochloric acid was added. 50mL of chloroform was added and the mixture was washed twice with water. The organic phase was rotary evaporated to remove the solvent, and the mixture was dried in petroleum ether: dichloromethane 2:1 (vol/vol) was used as eluent, and silica gel column chromatography was used to obtain the product in 78% yield.
Synthesis of target compound M3 target compound M3 was analogous to the synthesis of compound M2. The adopted catalyst is triethylamine, and the eluting agent adopts petroleum ether: chloroform was obtained in a mixed solvent of 1:2, and the yield of the obtained product was 60%.
Synthesis of optoelectronic Compound M4
Figure GDA0001113880950000232
Compound 10: the synthesis of compound 10 is similar to that of compound 8, and the eluent is petroleum ether: dichloromethane to 3:2 (vol/vol) gave a product yield of 70%.
Synthesis of target compound M4 target compound M4 was similar to the synthesis of target compound M3. The adopted catalyst is triethylamine, and the eluting agent adopts petroleum ether: chloroform in a mixed solvent of 1:2, the yield of the obtained product was 65%.
Example 3: and measuring the ultraviolet visible absorption spectrum of the small molecule M1-M4 in a chloroform solution and in a thin film state.
Dissolving a proper amount of M1 or M2 in chloroform to prepare a solution with a certain concentration, and taking part of the solution to spin-coat on a quartz plate to prepare a micromolecular film. The ultraviolet-visible absorption spectra of the compounds M1-M4 in chloroform solution and in thin film state are shown in FIGS. 1-4. It can be seen that M1-M4 has a very wide absorption in the visible region, and the film is red-shifted by about 80nm relative to the solution, indicating that the two have a very good aggregation effect in the film.
Example 4: measurement of cyclic voltammetry curve in small molecule film state
FIG. 5 is a cyclic voltammogram based on M1 and M2 films, and FIG. 6 is a cyclic voltammogram based on M3 and M4 films. And coating the chloroform solution on a platinum electrode, taking Ag/Ag + as a reference electrode, airing to form a film, and then placing the film in acetonitrile solution of tetrabutyl ammonium hexafluorophosphate for measurement. The initial oxidation potential and the initial reduction potential obtained from the graph are then represented by the formula EHOMOThe HOMO and LUMO levels of these two compounds were calculated as-e (Eonset ox +4.71) (eV), ELUMO ═ e (Eonset red +4.71) (eV). Specific values are shown in table 1. As can be seen from the table, each of the four materials has a lower highest electron occupied orbital (HOMO), providing a basis for obtaining a high open circuit for photovoltaic devices made based on these two materials.
Example 5: photovoltaic property testing of M1 and M2 based on forward device structures
Using M1 or M2 as donor, PC70BM prepares the organic solar cell device by solution spin coating for the receptor. The structure of the device is ITO/PEDOT, PSS/M1: PCBM/Ca/Al. Specific preparation methodThe following were used: mixing M1 or M2 with PC70BM blending (donor: PC)70BM mass ratio of 1.5:1) was dissolved in chloroform to prepare a solution of 10 mg/mL. Organic solar cells were fabricated on transparent silver tin oxide (ITO) coated glass substrates. And (2) sequentially ultrasonically cleaning the transparent conductive glass with the ITO by using deionized water, acetone and isopropanol for 15 minutes respectively, then treating the surface of the substrate by using ozone, spin-coating PEDOT (PSS) on the ITO at the rotation speed of 2000-6000 rpm, and drying at 150 ℃ for 15 minutes to obtain an anode modification layer with the thickness of 30 nm. Mixing small molecules with PC in a glove box70Uniformly spin-coating the solution on the anode modification layer by using a chloroform solution of BM at a rotation speed of 600-4000 rpm to obtain an active material layer with a thickness of 80-150 nm. Finally at 2X 10-6Evaporating Ca onto the active material layer under vacuum degree of Torr to form a cathode modification layer with a thickness of 20 nm; and is at 2X 10-6And evaporating Al onto the cathode modification layer under the vacuum degree of the support to form a cathode with the thickness of 100nm, thereby obtaining the micromolecule solar cell device. The combination of a 500W xenon lamp and an AM1.5 filter is used as a white light source for simulating sunlight, and the light intensity at the measuring position of the device is adjusted to 100mW/cm-2The prepared polymer solar cell device was tested for three parameters of open circuit voltage, short circuit current, and fill factor using Keithley. Fig. 7 and 8 are current-voltage plots based on molecular M1 and M2 devices, respectively. Table 2 shows the specific device performance parameters for M1 and M2.
Example 6: photovoltaic property testing of M3 and M4 based on inverted device structures
Using M3 or M4 as donor, PC70BM prepares the organic solar cell device by solution spin coating for the receptor. The structure of the device is ITO/ZnO/M3 or M4: PC (personal computer)70BM/MoOx/Ag. The preparation method comprises the following steps: mixing M3 or M4 with PC70BM blending (donor: PC)70BM mass ratio of 1.3:1) was dissolved in chloroform to make a solution of total concentration 18.5 mg/mL. Organic solar cells were fabricated on transparent silver tin oxide (ITO) coated glass substrates. Sequentially and ultrasonically cleaning transparent conductive glass with ITO (indium tin oxide) by using deionized water, acetone and isopropanol for 15 minutes, treating the surface of a substrate by using ozone, and treating ZnThe O precursor is coated on the ITO in a spinning way, the rotating speed of the spinning way is 2000-6000 rpm, and the cathode modification layer with the thickness of 20nm is obtained after annealing for 30 minutes at the temperature of 200 ℃. Mixing small molecules with PC in a glove box70Uniformly spin-coating the solution on the anode modification layer by using a chloroform solution of BM at a rotation speed of 600-4000 rpm to obtain an active material layer with a thickness of 80-150 nm. Finally at 2X 10-6Evaporating MoOx onto the active material layer under the vacuum degree of the support to form an anode modification layer with the thickness of 5 nm; and is at 2X 10-6And (3) evaporating Ag to the cathode modification layer under the vacuum degree of the support to form an anode with the thickness of 100nm, thereby obtaining the micromolecule solar cell device. The combination of a 500W xenon lamp and an AM1.5 filter is used as a white light source for simulating sunlight, and the light intensity at the measuring position of the device is adjusted to 100mW/cm-2The prepared polymer solar cell device was tested for three parameters of open circuit voltage, short circuit current, and fill factor using Keithley. Fig. 9 and 10 are current-voltage plots based on molecular M3 and M4 devices, respectively. Table 3 shows the specific device performance parameters for M3 and M4.
Table 1 HOMO and LUMO energy levels of the photovoltaic compounds M1-M4 were measured using cyclic voltammetry.
Figure GDA0001113880950000261
Table 2 forward device structure solar cell device performance based on photovoltaic compounds M1 and M2.
Figure GDA0001113880950000262
Table 3 inverse device structure solar cell device performance based on photovoltaic compounds M3 and M4.
Figure GDA0001113880950000271
In conclusion, the materials based on the description have high open-circuit voltage, the photoelectric conversion efficiency can reach 11.5%, additives and thermal/solvent annealing are not needed in the device preparation process, the device is simple to optimize, and the cost is greatly saved. And the organic micromolecule has definite structure, high purity and good reproducibility of material and device performance, so the organic micromolecule has potential to be suitable for large-area preparation and application.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (43)

1. An organic photovoltaic compound for a solar cell, having the structure shown in formula I below:
Figure FDA0002393571230000011
wherein the content of the first and second substances,
R1-R4independently selected from H, C1-C30Alkyl radical, C1-C30Alkoxy, mercapto, C1-C30Cycloalkyl and C1-C30An ester group;
X1、X2independently selected from the group consisting of sulfur, oxygen or selenium atoms;
d is a donor unit and A is an acceptor unit;
the donor unit is selected from one of the following structures:
Figure FDA0002393571230000012
wherein R is5Independently selected from C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy; x3、X4Is independently selected fromA sulfur, oxygen or selenium atom;
the acceptor unit is selected from one of the following structures:
Figure FDA0002393571230000021
wherein R is6Is selected from C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy.
2. The compound of claim 1, wherein the compound of formula I is selected from one of the following structures:
Figure FDA0002393571230000022
Figure FDA0002393571230000031
Figure FDA0002393571230000041
wherein R is1-R4Independently selected from H, C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy;
X1-X4independently selected from a sulfur, oxygen, or selenium atom.
3. The compound of claim 1 or 2, wherein the compound of formula I is selected from one of the following structures:
Figure FDA0002393571230000042
Figure FDA0002393571230000051
Figure FDA0002393571230000061
4. the method for producing the compound according to claim 1, wherein the compound is produced by subjecting a bisaldehyde-based terminal group compound and a terminal group acceptor unit to a kroneger condensation reaction;
the double aldehyde end group compound has the following structure:
Figure FDA0002393571230000071
the D, R1-R4、X1、X2、X3、X4All having the same limitations as defined in claim 1;
the terminal acceptor unit is selected from one of the following structures:
Figure FDA0002393571230000072
wherein R is6Is selected from C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy.
5. A process for the preparation of a compound according to claim 4, comprising the steps of:
(1) under the protection of inert gas, adding a pi-bridge monomer, a trimethyl tin substituted donor unit and a catalyst into an organic solvent, and heating for reaction to obtain a dialdehyde-based end group compound;
(2) adding the dialdehyde-based end group compound, the receptor unit and the catalyst into a solvent for reaction to obtain the target compound;
the structure of the pi bridge monomer is shown as the following formula II:
Figure FDA0002393571230000081
wherein the content of the first and second substances,
R1-R4independently selected from H, C1-C30Halogenated or non-halogenated alkyl, C1-C30Halogenated or non-halogenated alkoxy;
X1、X2independently selected from the group consisting of sulfur, oxygen or selenium atoms;
the trimethyl tin substituted donor unit is 1 of the following:
Figure FDA0002393571230000082
wherein R is5Is H, C6-C12Halogenated or non-halogenated alkyl, C6-C12Halogenated or non-halogenated alkoxy.
6. The method according to claim 5, wherein the inert gas in the step (1) is nitrogen or argon.
7. The process according to claim 5, wherein the catalyst in the step (1) is Pd (PPh)3)4。
8. The method according to claim 5, wherein the solvent in the step (1) is toluene.
9. The method of claim 5, wherein the molar ratio of the pi-bridge monomer to the trimethyltin-substituted donor unit is 2-4: 1.
10. The method according to claim 5, wherein the catalyst is used in a molar amount of 5 to 10% based on the amount of the pi-bridged monomer in the step (1).
11. The process according to claim 8, wherein the solvent toluene used in step (1) is 10 to 100mL/mmol relative to the trimethyltin-substituted donor unit.
12. The preparation method according to claim 5, wherein the heating reaction temperature is 80-100 ℃ and the reaction time is 12-48 h.
13. The process according to claim 12, wherein the reaction time is 24 to 48 hours.
14. The process according to claim 5, wherein the reaction mixture is concentrated and purified by column chromatography after the reaction in step (1) is completed.
15. The method according to claim 14, wherein the column chromatography uses a mixed solvent of dichloromethane and petroleum ether as an eluent.
16. The method according to claim 5, wherein the molar ratio of the dialdehyde end group precursor to the acceptor unit in the step (2) is 1: 1-15.
17. The method according to claim 5, wherein the catalyst in step (2) is one or a mixture of two or more of triethylamine, piperidine, and pyridine.
18. The method according to claim 5, wherein the catalyst is used in an amount of 5 to 20 mol% based on the dialdehyde terminal precursor in step (2).
19. The method according to claim 5, wherein the temperature of the reaction in the step (2) is 25 to 80 ℃ and the reaction time is 1 to 3 days.
20. The preparation method according to claim 5, wherein after the reaction in step (2) is completed, the reaction solution is concentrated, purified by a column, and then recrystallized to obtain the target compound.
21. The method according to claim 20, wherein the column chromatography uses a mixed solvent of chloroform and petroleum ether as an eluent.
22. The production method according to claim 20, wherein the recrystallization is carried out using a mixed solvent of chloroform and methanol.
23. The method of claim 5, wherein the pi bridge monomer is
Figure FDA0002393571230000101
Figure FDA0002393571230000102
1 kind of (1).
24. The method of claim 5, wherein the pi bridge monomer is one of the following structures:
Figure FDA0002393571230000103
25. the method of claim 5 or 24, wherein the pi-bridge monomer is prepared by coupling and rebromination of a boronic ester of a bithiophene or a diselenophene with a bromide of a monoaldehyde-substituted thiophene or selenophene.
26. The method of claim 25, wherein the pi-bridge monomer is prepared by a method comprising the steps of:
(1) under the protection of inert gas, reacting boric acid ester of bithiophene or boric acid ester of bithiophene with bromide of monoaldehyde substituted thiophene or selenophene, toluene, water and tetrahydrofuran,NaHCO3，Pd(PPh3)4adding a catalyst into a toluene solvent for reaction to obtain a mono-aldehyde coupled compound;
(2) and (2) adding N-bromosuccinimide into the mixed solution of the compound with the single aldehyde end group coupling obtained in the step (1), acetic acid and chloroform for reaction to obtain the pi bridge monomer.
27. The method according to claim 26, wherein the inert gas in the step (1) is nitrogen or helium.
28. The method of claim 26, wherein the molar ratio of the borate ester of the bithiophene or selenophene to the bromide of the monoaldehyde-substituted thiophene or selenophene is 1:1 to 2.
29. The process of claim 5, wherein the NaHCO is3The mol ratio of the bromide of the single aldehyde substituted thiophene or selenophene is 3-10: 1.
30. The method of claim 26, wherein Pd (PPh)3)4The molar amount of the compound is 2 to 10 percent of the bromide of the single aldehyde substituted thiophene or selenophene.
31. The method according to claim 26, wherein the toluene is used in an amount of 1 to 10mL/mmol relative to the monoaldehyde-substituted thiophene or selenophene.
32. The method of claim 26, wherein the ratio of toluene: water: the volume ratio of the tetrahydrofuran is 1:1: 1-10.
33. The method according to claim 26, wherein the temperature of the reaction in the step (1) is 30 to 90 ℃ and the reaction time is 1 to 7 days.
34. The method according to claim 26, wherein the reaction mixture is concentrated by washing with water and then purified by column chromatography after the reaction in step (1) is completed.
35. The method according to claim 34, wherein the column chromatography uses a mixed solvent of dichloromethane and petroleum ether as an eluent.
36. The method of claim 26, wherein the molar ratio of N-bromosuccinimide to the bromide of the monoaldehyde-substituted thiophene or selenophene in step (2) is 1-1.2: 1.
37. The method according to claim 26, wherein the volume ratio of acetic acid to chloroform is 0.1 to 3: 1.
38. The method as claimed in claim 26, wherein chloroform is used in an amount of 5 to 50mL/mmol with respect to the thiophene or selenophene having a single aldehyde group.
39. The method of claim 26, wherein the reaction in step (2) is carried out at a temperature of-10 ℃ to 25 ℃ for a time of 4 to 48 hours.
40. The preparation method according to claim 26, wherein after the reaction in the step (2) is completed, the reaction solution is subjected to extraction and washing with water, and then is subjected to column purification to obtain the target compound.
41. The method of claim 40, wherein the extraction is performed with chloroform.
42. The method according to claim 40, wherein the column chromatography uses a mixed solvent of dichloromethane and petroleum ether as an eluent.
43. Use of a compound according to any one of claims 1 to 3 in the field of photovoltaic devices, characterized in that it is used in solar cells as an active layer donor/acceptor material.
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